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While RDF and Microformats do have a lot in common, they are entirely different things. The purpose of RDF is to describe and mark-up META data and explain relationships between documents or elements and provide definitions of how they should relate to each other. Microformats on the other hand exist to give added semantic meaning to structured elements within the document flow using patterns and conventions to give added emphasis to the relevance of information. Technically speaking while RDF can include Microformats, they serve different purposes entirely.

RDF explains the relationship between data through descriptive defining.
Microformats explain the purpose of structured mark-up so that it can be differentiated from similar structure.